Manufacture of low boiling petroleum distillates



May 18, `1943 H. w. GROTE MANUFACTURE 0F LOW BOILING PETROLEUM DISTILLATES Fil-ed April 18, 1940 Patented May 18, 1943 MANUFACTURE 0F LOW BOlLlNG PETROLEUM DISTILLATES Henry W. Grote, Chicago, lll., asslgnor to Universal Oil Products Company, Chicago, Ill., a

corporation of Delaware Application April 18, 1940, Serial No. 330,253

(Cl. 19E-54) 4 Claims.

This invention relates to the manufacture of low boiling petroleum distillates comprising a process of catalytically cracking higher boiling petroleum fractions in the presence of anhydrous aluminum chloride. This process is advantageously applied to a hydrocarbon distillate such as a gas oil, lalthough it is not the purpose of the invention to 'be limited to such a charging stock.

As is well known, anhydrous aluminum chloride exerts several specific effects upon heated mineral oils. These effects include the severing of carbon-to-carbon bonds, resulting in a decyclization of naphthenes and isomerization of straight chain paraiins into compounds with iso structure, the net result of which is to form low boiling distillates which have the advantage of being saturated and at the same time having relatively high octane numbers: The process is well suited for the productionof saturated aviation fuels of good tetraethyl lead susceptibility, progasoline and light products and a side cut to be used as an absorbing oil as will be further descri-bed, and a residual fraction, subjecting said residual fraction to a catalytic cracking treatment with powdered 'aluminum chloride in a secondary cracking zone, directing the conversion products from said secondary cracking zone to ducing at the same time a gas consisting in large part of isobutane.

In general the best results are obtained by employing such contact timevas that which will give conversion of 10 to 25% by weight of gas plus gasoline per pass in the presence of 11/2 to 2% by weight of aluminum chloride based on the combined feed.. It has .been found advantageous to add a small quantity of anhydrous hydrogen chloride with the charge. The present invention comprises a continuous process of aluminum chloride cracking in which the catalyst is supplied in the form of a slurry and commingled with the feed for the heating coil. The process includes twc flash chambers, the used catalyst being rey moved in slurry form with a non-vaporous residue fromthe secondary flash chamber. A certain amount of anhydrous aluminum chloride, as well as its hydrocarbon complexes, are carried along in the vapors from the two flash chambers. This aluminum chloride has retained most of its activity and, according to the process of my invention, is returned in the form of a slurry to the cracking zone. In one specic embodiment the present invention comprises subjecting a combined feed formed as hereinafter described to the action of aluminum chloride catalyst in a primary cracking zone under such conditions as to form substantial quantities of gasoline. flashing the products of said catalytic` treatment jointly with the products from a second aluminum chloride cracking zone operating in a manner to be subsequently described, directing the vapors from said flashing process to fractionating process for separationl of the primary flash chamber for joint flashing with the products from the primary cracking zone as already described, directing the residual product from the primary dashing zone to a secondary dashing zone for further vaporization and for separation from the used catalyst, directing the vapors' evolved in said secondary flashing zone to a zone for cooling and condensation by commingling with the raw oil charging stock to form a combined feed for cracking by aluminum chloride in a primary cracking zone as already described, separating the unstabilized gasoline and gaseous products obtained as an overhead product in the fractionator from the vapors from the primary iiash chamber, stabilizing said gasoline to form a motor fuel of the desired vapor pres'- sure and a lighter fraction, separating from said lighter products a liquid fraction rich in isobutane, combining the remaining portion of said light products with the gases separated in the receiver for the unstabilized gasoline and directing said gaseous mixture with any vapors evolved in the internal condenser and cooler for the vaporous product from the secondary ilash chamber and subjecting the total cracked gaseous mixture to contact with an absorbing oil obtained in -a side cut from the fractionator for the vaporous products ofthe primary flash chamber, returning the rich absorber oil to said fractionator for the liberation of the cracked product.

These and other features of the present invention can be more readily described by referring to the accompanying drawing which represents diagrammatically various steps of the processes involved and the general nature of the equipment used to carry out the operations described. Raw oil for the process is removed from storage chamber i by way of line 2 containing control valve 3 and by means of pump 4 is directed to line 5. valve 6 from which it passes into fractionator l. This fractionator operates as an internal cooler and condenser for the vapors obtained from the secondary hashing chamber, the major portion of the vapors from said ilash chamber being condcnsed in column 1 giving up their heat to the incoming raw oil charging stock. The combined heated raw oil and condensed vapors from this secondary flash chamber are removed irom the column by way of line 8, valve 9 and by means of pump l are introduced through line II, valve I2 after which they are commingled with the aluminum chloride catalyst which is supplied in slurry form from container I3 by way of line I4, valve I5 through line IB, valve I1. The feed for the heating coil together with the catalyst is raised to a temperature Within the approximate range of 500 to 850 F. under a pressure of 'I0-400 pounds per square inch. 'Ihe heated oil is discharged from coil 92 through line I8 and after passing through valve I9 enters flash chamber 29 under a substantially reduced pressure of approximately -100 pounds per square inch. Flash chamber 28 operates for the joint flashing of the product from heater 92 as already described and for the product of heater 23, the operation of which will be discussed subsequently. The vaporous conversion products, together with the vapors from flash chamber 20 are removed by way of line 21, valve 28 and directed to fractionating column 29. Fractionating column 29 operates at substantially the same pressure as esh chamber 2D, a light vaporous fraction consisting of normally gaseous products and gasoline boiling range hydrocarbons being removed as an overhead product through line 38, valve 3| and directed to cooler and condenser 32 wherein the normally liquid hydrocarbons are condensed to form a distillate. solved and uncondensed gases leaving condenser 32 are directed through line 33, valve 34 to receiver 35 wherein the distillate gases are collected and separated. The distillate collected and separated in receiver 35 is removed by .way of line 36,

valve 31 and directed to line 38 from which a portion is returned to fractionator 29 for reuxing and cooling the upper portion thereof as will be further described. A portion of the distillate not so returned is directed by means of pump 39 to line 40, valve 4I from which it is supplied to stabilizer 42. stabilizing column 42, which may operate under a pressure of 100-300 pounds per square inch, produces a gasoline of the desired vapor pressure which is removed from the column as a bottoms product through line 43, valve 44 and is directed to cooler 45 from which it passes through line 46, valve 41 and is collected as a product of the process. The overhead from stabilizer 42 consists of normally gaseous hydrocarbons and is directed through line 48, valve 49 to cooler and condenser 5I) which operates to cool and condense the greater portion of said overhead product. Distillate leaving condenser 58 together with the undissolved and uncondensed gases is directed through line 5I valve 52 to receiver 53 wherein the undissolved and uncondensed gases are separated from the distillate. The distillate collected in the lower portion of receiver 53 is removed by Way of line 54, valve 55 and a portion directed to line 56 where by means of pump 51 it is directed to line 58, valve 59 to stabilizer 42 for cooling and reflux. The portion of the distillate not so returned is directed through line 68, valve 6I and is collected as a product of the process. It contains a large quantity of isoparains, particularly isobutane, and may constitute a valuable stock for such processes as alkylation or dehydrogenation to form aviation fuel.

The distillate together with the undis- The bottoms product obtained in fractionator 29 is removed by way of line 62, valve 63 and by means of pump 64 is directed to line 65, valve 56, after which it is commingled with powdered aluminum chloride catalyst supplied in a slurry through line 2 I, valve 22 and directed to heating coil 23 so disposed as to receive heat from furnace 24. Heating coil 23 operates under a pressure varying from 10 to 400 pounds per square inch. The charge leaves the heating coil at a temperature Within the range of approximately G50-900 F. and is directed by way of line 25, valve 26 to primary flash chamber 2U, operating at a pressure within the approximate range of 30-100 pounds per square inch, wherein it is flashed jointly with the conversion products obtained from the primary heating coil 92l as previously described. The liquid residue obtained from flash chamber 20 containing the used catalyst in suspension is removed by way of line 61, valve G8 and is directed to a secondary flash chamber 59 operating under a pressure varying from 5 to 50 pounds per square inch. The vapors formed in ash chamber 69 are removed by way of line 18, valve 1I and are directed to column 1 where they are coole-d and condensed by being commingled with the raw oil charging stock as previously described. The non-vaporous liquid residue obtained in flash chamber 69 containing spent catalyst in suspension is removed by way of line 12, valve 13. It may be regenerated by the action of air and chlorine, or by other methods well known in the art.

A small quantity of non-condensible gases not absorbed in fractionator 1 is removed by way of line 14, valve 15 and directed to line 16 wherein it is commingled with the gases removed from separator 35 by way of line 18, valve 19 and the stabilizer gases removed from receiver 53 by way of line 80, valve 8l. The combined gases go through valve 11 and pass into absorber 82 where they are subjected to contact with an absorbing liquid obtained as a side cut from fractionating column 29 from which it is removed by way of line 85, valve 86. The hydrogen and normally gaseous hydrocarbons in excess of that necessary to gases of desired vapor pressure is removed by way of line 83, valve 84 and collected as a product of the process. The liquid absorbing medium used in column 82 containing lighter hydrocarbons in solution is removed by way of line 81 and after passing through valve 88 is directed to line 38 commingling therein with a portion of the distillate removed from receiver 35 by way of line 36, valve 31, line 38 and valve 38'. by pump 89 through line 99 and valve 9| into fractionating column 29 for cooling and reux and for the liberation of the more volatile constituents.

The following example is given to illustrate the usefulness and practicability of my process but should not be construed as Hunting it to the exact conditionsindicated therein. A Trinidad gas oil is charged to the internal condenser and commingled with the vapors from the secondary flash chamber. This combined feed is subjected to cracking with 2% by weight of powdered aluminum chloride catalyst in the primary cracking zone at a temperature of 650 F. and a pressure of 200 pounds per square inch. The converted products of the primary reaction coil are ilashed jointly with the products from the secondary reaction coil in a primary ash chamber operated under a pressure of pounds per square inch. The vapors from the primary ash chamber are directed to a fractionating column operated under substantially the same pressure for the separation of gasoline boiling range hydrocarbons and lighter products, a side The resultant mixture is forced aus( 'cut which is used as an absorbing ou and returned to the column and a residual liquid portion which is commingled with 2% by weight of the aluminum chloride in the form of a slurry and directed to a secondary cracking zone operated at a temperature of l150 F. and a pressure of 200. pounds per square inch. 'Ihe products from this secondary cracking zone are ilashed as already described. The residual portion obtained from the primary4 ash chamber is directed to a secondary ilashchamber for further vaporiz'ation. This secondary flash chamber is operated under a pressure of 30 pounds per square inch, vapors formed in the flashing operation being separated from the liquid residue containing the used catalyst in suspension. Vapors from the secondary ash chamber are cooled and condensed by commingling with the raw oll as already described. A'yield of gasoline equal to 41% by volume of 300 end point,

having an octane number of 761/2 may be obwmtained. A total yield of 24% of butane containing 88% isobutane may be vobtained from V- the same operation.

I claim as my invention: Y l. A process for converting hydrocarbon'oils into valuable products including high antiknock gasoline which comprises subjecting a combined feed formed as hereinafter described tothe yaction of powdered aluminum chloride catalyst in a primary cracking zone under conditions of temperature and pressure adequateto produce substantial yields of motor fuel, supplying the reaction products to a primary flashing zone for joint flashing with reaction products obtained in a manner hereinafter described, directing vapors from said .primary flashing zone to a fractionating step for separation' into normally gaseous products, gasoline boiling range hydrocarbons-and higher boiling intermediate conversion products, subjecting at least a portion of said intermediate conversionprodu'cts to the action of powdered aluminum chloride in a secondary cracking zone, commingling the products from said secondary cracking zone with the' products from said primary cracking zone `for joint flashing as aforesaid, withdrawing non- 2. I'he process as set for-th in claim 1 wherein the primary cracking zone is operated at a temperature within the range of approximately 50o-850 F. and a pressure ywithin the range of approximately 'I0-400 pounds per square inch.

3. '.lhe process as setforthln claim 1 wherein the secondary cracking zone is operated at a temperature within the range of approximately G50-900 F. and a pressure within the range of 70-400 lpounds per square inch.l l

4. A conversion process which comprises passing a mixture of hydrocarbon oil and aluminum chloride catalyst in a restricted stream through a heating zone and subjecting the same therein to catalytic conversion conditions of temperature and pressure, discharging resultant products into an enlarged separating zone and therein separating vapors from residual catalyft-containing liquid, fractionating the vapors to condense heavier fractions thereof, passing resultant reflux condensate, together with additional aluminum chloride catalyst, through a second heating zone and. therein subjecting the same to 4independently controlled catalytic conversion conditions, discharging reaction' products and catalyst from said second zone into said separating zone for separation therein together with the rst-mentioned products, removing said catalyst-containing liquid from the separating zone and reducing the pressure thereon, thereby forming additional chloride, contacting said additional vapors with fresh charging oil for the process to condense at least a portion' thereof 'and the aluminum chloride, and supplying thus comminglcd charging oil, condensate and aluminum chloride to the first-mentioned heating zone. HENRY W. GROTE.

vapors containing aluminum 

